Diphenylamines for dyeing keratinous fibers

ABSTRACT

Diphenylamines of the formula   WHEREIN R1 and R2 each independently represent hydrogen, halogen or lower alkyl containing one to four carbon atoms with at least one of R1 and R2 being other than hydrogen; R3, R4, R5, R6, and R7 each independently represent hydrogen, methoxy, or lower alkyl optionally substituted with hydroxy, carbamyl, piperidinyl or acylamino; R3 and R6 or R4 and R7 also optionally forming together with the carbon and nitrogen atoms to which they are attached, a dihydrooxazine or pyrroline heterocycle; and Z represents amino, acylamino or hydroxy; and the acid salts of said diphenylamines. These diphenylamines are usefully employed in cosmetic compositions for the hair including hair dye compositions and hair setting lotion compositions.

United States Patent 1191 Kalopissis et al.

1451 Jan. 22, 1974 DIPHENYLAMINES FOR DYEING KERATINOUS FIBERS Inventors: Gregoire Kalopissis, Paris; Andree Bugaut, Boulogne-sur-Seine; Francoise Estradier, Paris, all of France Assignee: LOreal, Paris, France Filed: July 11, 1972 Appl. No.: 270,650

Related U.S. Application Data Continuation-impart of Ser. No. 61,833, Aug. 6, 1970.

Foreign Application Priority Data Aug. 11, I969 Luxembourg 59265 11.8. c1 8/11, 8/l0.2, 260/571, 260/573, 424/71 161. c1 D06p 1/32, C07C 91/42 Field of Search..... 8/102, 11, 32, 88; 260/571, 260/573; 424/71 References Cited UNITED STATES PATENTS 6/ 1933 Salzberg et al. 260/243 3/1937 Salzberg et a]. 424/250 2/1971 Charle ct al. 8/11 Primary Examiner-Donald Levy Assistant ExaminerBruce H. Hess Attorney, Agent, or Firm-John W. Malley et a1.

[5 7] ABSTRACT Diphenylamines of the formula N NH zinc or pyrroline heterocycle; and Z represents amino,

acylamino or hydroxy; and the acid salts of said diphenylamines. These diphenylamines are usefully employed in cosmetic compositions for the hair including hair dye compositions and hair setting lotion compositions.

15 Claims, No Drawings DIPHENYLAMINES FOR DYEING KERATINOUS FIBERS This application is a continuation-in-part of our application Ser. No. 6l,833, filed Aug. 6, 1970.

This invention relates to novel leuco derivatives of indoanilines, a process for preparing the same and to novel cosmetic compositions containing these leuco derivatives for dyeing keratinic fibers such as human hair. The leuco derivatives of indoanilines of this invention are colorless compounds which when applied in an aqueous solution to the fibers to be dyed, oxidize in the air or in the presence of another oxidizing agent thereby giving the corresponding indoanilines, which on the other hand are colored compounds directly responsible for dyeing of the fiber. The dyes thus obtained present qualities of fastness and intensity of dyeing superior to those dyeings obtained by' direct application of indoanilines, because of the better solubility of the leucoderivatives of these compounds.

More specifically, the present invention relates to a compound of the formula:

wherein R. and R each independently represent a member selected from the group consisting of hydrogen, halogen, and lower alkyl containing one to four carbon atoms, with the proviso that at least one of R.

and R is other than hydrogen; R R and R each independently are selected from the group consisting of hydrogen, methozy, lower alkyl containing one to four carbon atoms and lower alkyl containing one to four carbon atoms and substituted with a member selected from the group consisting of hydroxy, carbamyl, piperidinyl and acylamino; R is selected from the group consisting of hydrogen, lower alkyl containing one to four carbon atoms, lower alkyl containing one to four carbon atoms and substituted with a member selected from the group consisting of hydroxy, carbamyl, piperidinyl and acylamino, and together with R and the nitrogen atom to which R is attached form a heterocycle selected from the group consisting of dihy-j drooxazine and pyrroline; R is selected from the group consisting of hydrogen, lower alkyl containing one to four carbon atoms, lower alkyl containing one to four carbon atoms and substituted with a member selected from the group consisting of hydroxy, carbamyl, piperidinyl and acylamino, and together with R and the nitrogen atom to which R, is attached form a heterocycle selected from the group consisting of dihydrooxazine and pyrroline; Z represents a member selected from the group consisting of amine, acylamino and hydroxy and the salts formed by these compounds with organic or inorganic acids, in particular, their oxalates, hydrochlorides or tartrates.

The novel diphenylamines according to the invention can be obtained by two different processes.

The first process comprises reducing the corresponding indoanilines of the formula whaehfiift oliiand Z have the meaning indicated :above, said reduction being performed either in an iaqueous alkaline medium with a reducing agent such as isodium hydrosulfite or ammonium sulfide, or in a solvent such as an alcohol, for instance, ethanol, by catalytic hydrogenation at ambient pressure in the presence, for example, of palladium on barium sulfate on on carbon.

When the process is carried out in an aqueous alkaline medium, the pH of said medium ranges generally between about 9-12, said pH having been attained generally by the inclusion therein of an alkalinizing agent such as sodium hydroxide or the like. The amount of reducing agent employed can vary but generally it will be present in amounts such that the mole ratio of indoaniline being reduced to reducing agent ranges between l:l.5 to 1:3. This reducing reaction is generally carried out at ambient pressure and at a temperature ranging from about 25 to 50C.

Alternatively, the reduction of the above indoaniline can be carried out in a solvent selected from the group consisting of ethanol and ethylacetate by catalytic hydrogenation at the ordinary pressure and a temperature of 20 to 50 in the presence of catalytic amounts of palladium on a substrate selected from the group consisting of barium sulfate and carbon. Generally, the amount of the catalyst, i.e., the palladium on said substrate, ranges between about 10 to 25 percent by weight of the indoaniline being reduced.

The second process, which makes it possible to obtain the diphenylamines of formula (I) wherein radicals R and R both designate a hydrogen atom, and Z in NH comprises condensing a dinitro derivative of the formula:

Illa N02 OzN wherein R, and R have the meaning given above, thereby obtaining a dinitrodiphenylamine of the formula:

OzN 011 which is then reduced by sodium hydrosulfite in an alkaline medium or by catalytic hydrogenation in a suitable solvent, such as an alcohol, for instance, ethanol. In this second process the molar ratio of said dinitro derivative to said substituted paraaminophenol is generally of l l and the condensation reaction is ordinarily carried out at the reflux temperature of the used solvent and at the ordinary pressure.

The reduction of the resulting dinitrodiphenylamine can, as stated above, be carried out in an aqueous alkaline medium having a pH ranging from about 9 to 12, the pH having been attained generally by the inclusion therein of an alkalinizing agent such as sodium hydroxide or the like. This reducing reaction is generally carried out at ambient pressure and at a temperature ranging from about 30 to 60 C.

Alternatively, the reduction of the above dinitrodiphenylamine can be carried out in a solvent such as ethanol by catalytic hydrogenation at the ordinary pressure and a temperature of 20 to 50 in the presence of catalytic amounts of palladium on a substrate selected from the group consisting of barium sulfate and carbon. Generally the amount of the catalyst, i.e., the palladium on said substrate, ranges between about 10 to 25 percent by weight of the dinitrodiphenylamine being reduced.

The diphenylamines of the present invention are usefully employed to dye keratinous fibers, particularly human hair.-When applied to human hair, these compounds, in an aqueous or dilute alcohol solution having a pH ranging from 4 to l l, and in extremely slight concentrations because of their good affinity for keratinous fibers and the power of the dyes obtained after oxidation either in the air or by another oxidizing agent such as hydrogen peroxide, provide an extremely rich range of shades ranging from very luminous violets to ash or silver grays passing through blues, greens, reds, pinks and golden, copper or ash blonds. The dyeings thus obtained are always characterized by their richness in glints and the pearly appearance they impart to the hair.

Thus, the present invention also relates to a dyeing composition for keratinous fibers, particularly human hair, comprising an aqueous or dilute alcohol solution of at least one compound of formula (I) ofa salt ofsuch a compound.

The dyeing compositions according to the invention can contain only the compounds of formula (I). However, they can also contain other known leuco derivatives of indoanilines, indamines or indophenols, or again oxidation dyes, such as oor pphenylenediamines or 0- or p-aminophenols or again direct dyes.

The concentration of the compounds of formula (I) in the dyeing composition according to the present invention can vary between 0.002 and 2 percent and generally between 0.005 and 0.5 percent by weight.

The pH of the dye compositions according to the present invention can vary between 4 and l I. To regulate this pH at the desired value, there can be used as the alkalizing agent, ammonia, mono-, dior triethanolamine, and as an acidifying agent phosphoric acid, acetic acid or lactic acid.

The dye composition according to the present invention is generally in the form of an aqueous solution, to which most often a low molecular weight alcohol, such an ethanol or isopropanol, has been added in a proportion of to 70 percent by weight. Rather than a low molecular weight alcohol a glycol, such as propyleneglycol or butylglycol, can be employed in amounts of about 1 to 6 percent by weight. The alcohol or the glycol facilitate putting the diphenylamines into solution.

Dyeing of the keratinous fibers, and particularly human hair, with the dye compositions of the present invention is performed in the usual way by applying said composition to the fibers to be dyed, said composition being left in contact with the fibers for a time varying from 10 to 30 minutes. Following this application the fibers can be rinsed and if desired, washed. Thereafter, the thus treated fibers are dried. If a simultaneous bleaching of the fiber is desired, there can be added to the composition, before its application, either hydrogen peroxide in amounts of 20 to 60 percent in weight of hydrogen peroxide of 20V that is to say 4 to 12 percent in weight of O H or an equivalent quantity of another oxidizing agent of said composition.

Tn another embodiment of the present invention, the novel diphenylamines can also be employed in the production of capillary hair-setting lotions. These lotions comprise an aqueous alcohol solution, at least one diphenylamine of Formula I or a salt thereof and at least one cosmetic resin. The amount of diphenylamine or its salt, as defined above, present in the hair-setting lotion according to this invention can be extremely slight. Such an amount generally varies between 0.002 and 1 percent by weight and preferably between 0.002 and 0.5 percent by weight of the total hair-setting lotion composition, the pH of which generally lies between 5-8.

Representative cosmetic resins that can be employed in the hair-setting lotions of the present invention in clude, for instance, polyvinyl pyrrolidone having a molecular weight of 40,000-400,000, copolymer of crotonic acid and vinyl acetate, said copolymer having a molecular weight ranging from about 10,000 to 70,000, copolymer of vinyl pyrrolidone and vinyl acetate wherein the ratio of PVP to VA ranges between 50-70:50-30, said copolymer having a molecular weight ranging from about 30,000 to 200,000 and maleic anhydride-butylvinyl ether copolymer, a 1 percent solution of which in methylethyl ketone has a viscosity of 0.1-3.5 cps at 25C. These resins are used in a proportion of about 1 to 3 percent by weight of the hairsetting lotion composition.

The alcohols suitable for the preparation of the hairblue or pink. The coloring obtained are characterized by a pearly appearance and a great richness of glints and by their regularity or evenness even in the case of application to irregularly bleached hair.

The hair-setting lotions according to the invention are usually employed by application to wet hair, previously washed and rinsed, followed by rolling the hair up on curlers and drying the hair.

The following examples are intended to illustrate the present invention. Unless otherwise specified all parts and percentages are by weight and all temperatures are expressed in degrees centigrade.

EXAMPLE 1 4-hydroxy 3,5'-dimethyl 2', 4'-diamino diphenylamine is prepared according to the following reaction:

NH; CH3 mnQ-zsGo-not NH; cm

HzNQ-NHQOH 0.0086 mole (2.41 g) of sodium hydrosulfite of 75 percent purity, is dissolved in 27.5 cc of a 0.5 N soda solution. To this solution, 0.00342 mole (0.950 g) of N-[(2,4-diamino Smethyl) phenyl] 3-methyl benzoquinone imine hydrochloride in suspension in 5 cc of 95 ethanol is added gradually, with stirring, keeping Analysis Calculated for Found 01 N01 HOQM.

H II II EXAMPLE 2 4-hydroxy 3-ch1oro 2,4'-diamino diphenylamine and its dihydrochloride, monohydrate are prepared as follows:

NHz Cl First phase Preparation of 4-hydroxy 3-chloro 2,4'- dinitro diphenylamine OH N O -NO2 Into 65 cc of absolute ethanol there are introduced, on the one hand, 0.025 mole (4.5 g) of 2-ch1oro 4- amino phenol hydrochloride, and, on the other hand, 0.025 mole (5.06 g) of 2,4-dinitro chlorobenzene and 6.2 g of molten sodium acetate. The mixture is brought to reflux, with stirring, for 6 hours then filtered while boiling to eliminate the inorganic salts.

50 cc of water are then added to the alcohol filtrate which is then cooled to 0C. 4-hydroxy Z-methyl 2,4'- dinitro diphenylamine, which precipitates, is filtered therefrom and this product, after washing in water, recrystallization in an ethanol-water mixture and drying under vacuum, melts at 189.

Second phase Preparation of 4-hydroxy 3-ch1oro 24diamino diphenylamine 0.07 mole (20 g) of sodium hydrosulfite of percent purity is dissolved in cc of normal soda solution. To this solution there is added gradually, with good stirring, while keeping the temperature in the vicinity of 35C, 0.009 mole (2.79 g) of the dinitro derivative previously obtained in the first phase above. When the addition is completed and the reaction mixture colorless, it is neutralized with acetic acid thereby precipitating the above diphenylamine.

After filtering this diphenylamine from the reaction mass, washing with water and drying it under vacuum, the product melts at 203.

Analysis Calculated for Found C H N OCI 1 g of this diphenylamine thus obtained is then dissolved in 5 cc of a 2 N hydrochloric solution. The resulting solution is cooled to -l0. Then 15 cc of hydrochloric acid at 22B are added. The 4-hydroxy 3-chloro 2',4'-diamino diphenylamine dihydrochloride, monohydrate crystallizes. After filtering and drying under vacuum for 3 hours, it melts with decomposition at 225".

Molecular weight calculated for C H N OCI'ZHCL H O =340.5

Molecular weight found by potentiometric determination in water with 0.1 N soda solution =343 EXAMPLE 3 4-hydroxy 2-methyl 2',4'-diamino diphenylamine is prepared in accordance with the following reaction:

First phase Preparation of 4-hydroxy 2-methyl 2, 4-dinitro diphenylamine.

into 65 cc of absolute ethanol there are introduced, on the one hand, 0.025 mole (5.1 g) of 3-methyl 4- amino phenol hydrobromide, and, on the other hand, 0.025 mole (5.06 g) of 2,4-dinitro chlorobenzene and 6.2 g molten sodium acetate. The resulting mixture is brought to reflux and kept there with stirring for four hours, after which it is filtered while boiling to eliminate inorganic salts. 50 cc of water are then added to the alcohol filtrate which is then cooled to C. 4- hydroxy Z-methyl 2', 4'-dinitro diphenylamine, which has precipitated, is then filtered therefrom. This product, after washing with water, recrystallization in an ethanol-water mixture and drying under vacuum, melts at 165.

CHJCOONB Second phase Preparation of 4-hydroxy 2-methyl 2',4'-diamino diphenylamine 0.071 mole (20 g) of sodium hydrosulfite of 75 percent purity is dissolved in 140 cc of normal soda solution. 0.0103 mole (3 g) of the dinitro derivative obtained in the 1st phase is then gradually added to this solution with good stirring, while keeping the temperature in the vicinity of 35C. When the addition is completed and the reaction mixture is colorless, it is neutralized with acetic acid thereby precipitating the above diphenylamine which is then filtered, washed with water and dried under vacuum five hours at 80. 1.94 g of this pure product, which melts at 163 are thus obtained.

EXAMPLE 4 4-hydroxy 3-methyl 5'-methoxy 2',4'-diamino diphenylamine is prepared in accordance with the following reaction:

To 160 cc ofa 1.25 N soda solution containing in solution 0.05 mole (14 g) of sodium hydrosulfite of percent purity there is added gradually, with good stirring and keeping the reaction mixture in the vicinity of 30C, 0.02 mole (5.87 g) of N-[(2,4-diamino 5- methoxy) phenyl] 3-methy1 benzoquinone imine hydrochloride in suspension in 30 cc of ethanol at 95. When the addition is finished and the reaction mixture is completely colorless, rapid filtering under nitrogen is performed, followed by neutralizing with acetic acid to precipitate the above diphenylamine. This diphenylamine product is isolated by filtering, after which it is washed with water and then dried 5 hours under vacuum at 4.3 g of chromatographically pure product, which melts at 204 are then obtained.

Molecular weight calculated for C H N O =259 Molecular weight found by potentiometric determination in acetic acid by perchloric acid =260 4-hydroxy 2-chloro 2,4'-diamino diphenylamine is prepared in accordance with the following reaction:

NHz C1 HINQIKTF NH2 Cl To 160 cc of a 1.25 N soda solution in which has been dissolved 0.05 mole (14 g) of sodium hydrosulfite of 75 percent purity there is added gradually, with good stirring. 0.02 mole (5.95 g) of N-[(2,4-diamino) phenyl] 2-ch1oro benzoquinone imine in suspension in 40 cc of ethanol at When the addition is finished, the reaction mixture is kept at 35C until total loss of fiiihafifigfii r0653 bypimibhiiric determination in acetic acid by perchloric acid =252 Calculated for C H N 0C1 Analysis Found EXAMPLE 6 4-hydroxy 2,6,3',5-tetramethyl 2',4'-diamino diphenylamine is prepared in accordance with the following reaction:

CH; N H2 CH:

CH3 CH3 CH3 N H2 CH! CH: (EH:

0.05 mole (14 g) of sodium hydrosulfite of 75 percent purity is dissolved in 150 cc of 1.25 N soda. To this solution there is added gradually, with good stirring, keeping the temperature in the vicinity of C, 0.02 mole (5.38 g) of N-{(2',4-diamino 3,5-dimethyl) phenyl]2,6-dimethyl benzoquinone imine in suspension in 40 cc of ethanol at 95. The reduction reaction is rather slow. However, when the reaction mixture is colorless, it is neutralized with acetic acid thereby precipi- 4 tating the above diphenylamine which is then filtered, washed with water and dried under vacuum for 5 hours at 80. 5.01 g of this pure diphenylamine, which melts at 250, are thus obtained.

Molecular weight calculated for C H N O =27] Molecular weight found by potentiometric determination in acetic acid by perchloric acid =273 Analysis Calculated Found CIGHIINIIO ca 70.82 70.43 70.55 HZ 7.80 7.43 7.81 N% 15.49 15.33 15.51

EXAMPLE 7 Second method of preparing the 4-hydroxy 2,6,3',5- tetramethyl 2,4-diamino diphenylamine described in Example 6:

0.027 mole (0.74 g) of N-[(2',4'-diamino 3',5'-- dimethyl) phenyl] 2,6-dimethyl benzoquinoneimine is dissolved in 45 cc of water and 30 cc of ethyl alcohol. To this resulting solution there are added gradually at 25, with stirring, 3.5 cc of an ammonia solution at l6Be previously saturated with sulfurated hydrogen. The completely colorless reaction mixture is then cooled at 0, thereby precipitating the above diphenylamine which is then filtered and washed with water. There is thus obtained, after drying the said diphenylamine under vacuum at 0.65 g of the pure product which melts at 250 and which is identical with the product prepared in Example 6.

EXAMPLE 8 4-hydroxy 3,5,3',5-tetramethyl 2,4-diamino diphenylamine and its dihydrochloride are prepared as follows:

0.01 mole (3.05 g) of N-[(2,4'-diamino 3',5- dimethyl) phenyl] 3,5-dimethyl benzoquinoneimine hydrochloride is dissolved in cc of water and 60 cc of ethanol. To this dilute alcohol solution there are added, drop by drop, with stirring and at 25, 9 cc of a an aqueous ammonia solution at l6Be previously saturated with sulfurated hydrogen. The reaction mixture becomes colorless. It is then cooled to 0, and the above diphenylamine which precipitates is filtered therefrom and washed with water. After drying the same under vacuum, 2.5 g of pure product, which metls at 167, are obtained.

Analysis Calculated for Found CIBHZIN3O 0% 70.82 70.02 i l 70.75 H% 7.80 7.89 7.76 N% 15.49 15.63 V M 15.47 W

quently with a little acetone. Thereafter the product is dried for three days under a nitrogen atmosphere. It melts with decomposition at 225. Molecular weight calculated for C l-I NQ'ZHCl 344 Molecularweight found by potentiometric determination in water with a 0.1 N soda solution =344 EXAMPLE 9 4-hydroxy 3-methyl 2',4'-diamino diphenylamine is prepared in accordance with the following reaction:

CH3 N02 S20 NB2-2H20 NaOH This dinitro diphenylamine after washing with water,-

recrystallized, in alcohol and drying under vacuum, melts at 176.

Analysis Calculated for Found w u n s Second Phase: Preparation of 4-hydroxy 3-methyl 2,4'-diamino diphenylamine 0.0714 mole (20 g) of sodium hydrosulfite of 75 percent purity is dissolved in 225 cc or normal soda solution. To this solution there is added gradually, with good stirring, while keeping the temperature in the vicinity of 55, 0.0138 mole (4g) of the dinitro diphenylamine obtained in the first phase. When the addition is completed and the reaction mixture is colorless, it is cooled. Then acetic acid is added to it until the pH equals 7.5, thereby precipitating the above diphenylamine which is then filtered, washed with water, and recrystallized in a dimethylformamide-water mixture. 2 g of pure product, which melts at 193, are obtained after having been dried under vacuum for 5 hours at 80. Molecular weight calculated for C 11 N =229 Molecular weight found by potentiometric determination in acetic acid by perchloric acid =232 Analysis Calculated for Found H IS CI ca 68.10 7 67.95 68.15 W H; 6.59 6.70 6.60 N; 18.33 18.33 18.30

EXAMPLE 10 4-hydroxy 2,3,3, '-t etramethyl 2 ,4 -di amin o d i phenylamine is prepared in accordance with the following reaction:

To 160 cc of a 1.25 N soda solution containing in solution 0.05 mole (14 g) of sodium hydrosulfite of percent purity there is added, gradually, with good stirring, while keeping the reaction mixture in the vicinity of 30, 0.02 mole (5.38 g) of N-[(2',4-diamino 3',5'-

dimethyl) phenyl] 2,3-dimethyl benzoquinoneimine partially dissolved in 50 cc of 95 ethanol. When the addition is completed and the reaction mixture is colorless, it is rapidly filtered under nitrogen and, after neutralizing with acetic acid, the above diphenylamine, which has precipitated, is filtered therefrom. After washing the said diphenylamine with water and drying it under vacuum at for 5 hours, the product (4.8 g) melts at c u N o 271 166. Molecular weight calculated for Molecular weight found by potentiometric determination in acetic acid by perchloric acid 274 4-hydroxy 3-methyl 2'-amino N,N-dimethylamino-4 diphenylamine is prepared in accordance with the following r e a ction:

0.025 mole (7 g) of sodium hydrosulfite of 75 percent purity is dissolved in 80 cc of a 1.25 N soda solution. To this resulting solution there is added gradually, with stirring, while keeping the temperature in the vicinity of 30, 0.01 mole (2.91 g) of N-[(2-amino 4- dimethylamino) phenyl] 3-methyl benzoquinoneimine hydrochloride in solution in 30 cc of water. When the addition is completed, the reaction mixture is allowed to become totally colorless. The acetic acid is added to pH 7 to precipitate the above diphenylamine which is then filtered under nitrogen, washed with water and dried under vacuum for 5 hours at 80. 2.35 g of the pure diphenylamine which melts at 187 are thus obtained.

Molecular weight calculated for C H N O 257 Molecular weight found by potentiometric determinat i& in acetic acid l perch1oric acid 258 4-hydroxy 3,3, S-trimethyl 2, 4'-diamino diphenylamine is prepared in accordance with the following reaction: w..-

cm NH: CH3

at 80 for hours. 5.42 g of pure product, which melts at 210, are thus obtained. Molecular weight calculated for C, H N O 271 Molecular weight found by potentiometric determination in acetic acid by percholoric acid 271 7 Analysis Calculated for Found IS IT Q I c% 66.43 66.2 1 7 65,93 31% 6.27 6.24 6.33 N% 15.49 15.30 15.52 W

EXAMPLE l4 4-hydroxy 3,5-dimethyl 2-amino 4-dimethylamino diphenylamine is prepared in accordance with the following reaction;

on, NE; on,

0.175 mole (4.9 g) of sodium hydrosulfite of 75 percent purity is dissolved in 50 cc of 1.25 N soda solution. To this resulting solution there is added gradually, with stirring, while keeping the temperature in the vicinity of 30, 0.007 mole (1.78 g) of N-[(2', 4-diamino 3, 5'-dimethyl) phenyl] B-methyl benzoquinoneimine in cc of 95 ethanol. When the addition is completed, the reaction mixture very rapidly becomes colorless. Then acetic acid is added to it until neutralization thereby precipitating the above diphenylamine which is then filtered under nitrogen, washed with water and dried under vacuum for 5 hours at 80. 0.84 g of the pure product, which melts at 141, is thus obtained.

Calculated for C" "I -3 Analysis Found mine in 20 cc of 95 ethanol. When the addition is completed, the stirring is kept up for about 30 minutes until total loss of color of the reaction mixture. The acetic Molecular weight calculated for C H ,N O =27l Molecular weight found by potentiometric determination in acetic acid by perchloric acid 273 Analysis H alculated for H CH:

0.05 mole (14 g) of sodium hydrosulfite of 75 percent purity is dissolved in cc ofa 1.25 N soda solution. To this resulting solution there is added gradually, :with stirring, while keeping the temperature in the vicinity of 30, 0.02 mole (6.11 g) of N-[(6'-amino loxa 4-aza l, 2, 3', 4-tetrahydro)7-naphthyl] 3- methyl benzoquinoneimine hydrochloride dissolved in 230 cc of ethanol and 10 cc of water. When the addition is completed, the reaction mixture is colorless. Then iucetic acid is added to it to pH 7 thereby precipitating the above diphenylamine which is then filtered under initrogen, washed with water and dried under vacuum Found w mM C% 70.82 70.35 70.43 H71 7.80 7.77 7.69 N7r l5.49 l5.37 15.54

EXAMPLE l5 4-hydroxy 2,5'-dimethyl 2', 4'-diamino diphenylamine is prepared in accordance with the following reaction:

thereby precipitating the above dinitro diphenylamine which is then filtered, 1.2 g of 4-hydroxy 2,5'-dimethyl 2',4-dinitro yielding 1.2 g of the same, which, after recrystallization in an ethanol-water mixture and drying under vacuum, melts at 168.

Analysis Calculated for Found H lfil fl ll Second phase. Preparation of 4-hydroxy 2,5-dimethyl 2',4-diamino diphenylamine 0.02 mole (4.64) of sodium hydrosulfite of 75 percent purity is dissolved in 35 cc of normal soda solution. To this solution there is gradually added, with good stirring, while keeping the temperature in the vicintity of 55, 0.003 mole (l g) of the dinitro diphenylamine previously obtained in the first phase above. When the addition is completed and the reaction mixture is colorless, it is cooled. Then acetic acid is added to it until neutralization to precipitate the above diphenylamine which is then filtered, washed with water and dried under vacuum. 0.4 g of pure product, which melts at 153, is thus obtained.

. Analysis Calculated for Found C H N O 0.5 H

C7 66.63 67.00 66.98 .H7r 7.20 7.29 7.21

EXAMPLE 16 4-hydroxy 2,3',5-trimethyl 2,4'-diamino diphenylamine and its dihydrochloride, monohydrate are prere s ems; We

0.01456Ibte (4.09 g) of sodium hydrosulfite of 75 trality to precipitate the above diphenylamine which is then filtered under nitrogen, washed with water and recrystallized in a dimethylformamide-water mixture. 0.90 g of pure product, which melts at 204, is obtained.

Molecular weight calculated for C l-1191430 257 Molecular weight found by potentiometric determination in acetic acid by perchloric acid 255 Analysis Calculated for Found CISHIHNJO 0.20 g of the diphenylamine thus obtained is dissolved in 5 cc of hydrochloric acid (d 1.19) at 25. The hydrochloric solution is cooled to 10. The 4- hydroxy 2,3',5-trimethyl 2',4-diamino diphenylamine dihydrochloride monohydrate crystallizes and it is filtered and dried under a nitrogen atmosphere. This resulting product melts with decomposition at 214. Molecular weight calculated for C H N O'H O'2HCl 348 Molecular weight found by potentiometric determination in water, with 0.1 N soda solution 2 352 EXAMPLE l7 4-hydroxy 3-ch1oro 2, 4-diamino 5-methoxy diphenylamine is prepared in accordance with the following reaction:

NH: Cl

NH: C1

. less, acetic acid is added to it to neutrality thereby precipitating the above diphenylamine which is then filtered under nitrogen, washed with water and dried under vacuum at for 5 hours. 2.50 g of pure product, which melts at are thus obtained.

Molecular weight calculated for C H N O Cl 279.5 Molecular weight found by potentiometric determination in acetic acid by perchloric acid 278 4-hydroxy 2-ch1oro 2',4'-diamino 5'-methoxy diphenylamine is prepared in accordance with the following reaction:

(i)CHa 0.025 mole (7 g) of sodium hydrosulfite of 75 percent purity is dissolved in 72 cc of 1.25 N soda solution. To this resulting solution, there is gradually added, with stirring, and while keeping the temperature in the vicinity of 30, 0.01 mole (2.77 g) of N-[(2,4'-diamino 5'- methoxy) phenyl] 2-chloro benzoquinoneimine in .cc of 95 ethanol. When the addition is completed, the reaction mixture is allowed to become completely colorless. Acetic acid is then added to it until neutrality thereby precipitating the above diphenylamine which is then filtered under nitrogen, washed with water and dried 3 days under vacuum on P 0 2.1 g of pure product, which melta at 137 are obtained.

Molecular weight calculated for C,,,H N O Cl 279.5

Molecular weight found by potentiometric determination in acetic acid by perchloric acid 281 Analysis Calculated for Found CIDHHNIXOQCI C7! 55.82 55.97 55.69 H7( 5.04 4.92 4.94 N71 15.02 15.20 14.92

EXAMPLE l9 4-hydroxy 3,6,3,5-tetramethyl 2',4'-diamino diphenylamine is prepared as follows:

: 0.0167 mole (4.62 g) of sodium hydrosulfite of 75 .percent purity is dissolved in 48 cc ofa 1.25 N soda sorlution. To this resulting solution there is added gradually, with stirring, while keeping the temperature in the land dried for 2 days on P 0 1 g of the pure productj lwhich melts at 153, is thus obtained.

Molecular weight calculated for C l-l N O =27l 'Molecular weight found by potentiometric determina- Ftion in acetic acid by perchloric acid =274 Analysis Calculated for Found iu ar a NO/O [5.49 |5.73 15.54

T EXAMPLE 20 4-hydroxy 2 riiethyl 2'-a cetylamino 4-amino diphenylarnine is prepared in accordance with the following reaction:

0.025 mole of sodium hydrosulfite of percent purity (7 g) is dissolved in 72 cc of 1.25 N soda solution. To this resulting solution there is gradually added, with stirring, while keeping the temperature in the vicinity of 30, 0.01 mole (3.05 g) of N-[(2'-acetylamino 4'- amino) phenyl] 2-methyl benzoquinoneimine hydrochloride dissolved in 15 cc of ethyl alcohol and 10 cc of water. The reaction mixture very quickly becomes colorless. Acetic acid is then added to it to neutralize the same, thereby precipitating the above diphenylamine which is then filtered, washed with water and dried under vacuum. After recrystallization in a dimethylformamide-water mixture and drying under vacuum, the product melts at 210.

Analysis Calculated for Found lZz l'i Il 2 C% 66.40 65.98 66.l2 H7: 6.32 6.27 6.35 w. 15.49 15.57 15.68

EXAMPLE 21 4-hydroxy 3,5 -dimethyl 2-acetylamino 4- dimethylamino diphenylamine is prepared in accordance with the following reaction: A

0.025 mole (7 g) of sodium hydrosulfite is dissolved in 75 cc of a 1.25 N soda solution. To this resulting solution there is gradually added, with stirring and while keeping the temperature in the vicinity of 30, 0.01 mole (3.29 g) of N-[(2-acetylamino 4- dimethylamino) phenyl] 3,5-dimethyl benzoquinoneimine monohydrate in 15 cc of ethanol. When the addition is completed, the mixture is allowed to become completely colorless. Acetic acid is then added to it until neutrally thereby precipitating the above diphenylamine which is then filtered, washed with water, recrystallized in a dimethylformamide-water mixture, and dried for 5 hours under vacuum, yielding 1.83 g of 19 pure product, melting M l 97. ,Molecular weight calculated for C ,,H N O =3l3 Molecular weight found by potentiometric determina tion in acetic acid by perchloric acid =309 4-hydroxy 3-chloro 2'-acetylamino 4'-amino 5'-' methyl diphenylamine is prepared in accordance with the following reaction:

NHCOCH: Cl

SHNHi HzN- N -O NHCOCH: Cl

HrN NH OH 0.0025 mole (0.759 g) of N-[(2'-ac e tylamiiio4' amino 5-methyl) phenyl] 3-chloro benzoquinoneimine is dissolved in 45 cc of water and 30 cc of ethyl alcohol. To this dilute alcohol solution there is added, drop by drop, with stirring and at 25', 2 cc of an aqueous ammonia solution at l6Be, previously saturated with sulfurated hydrogen. After 30 minutes, the reaction mixture is colorless. It is then cooled to and the above diphenylamine precipitates which, in turn, is filtered and washed with water. After recrystallization in adimethylformamide-water mixture, 0.40 g of pure product, which melts at 206, is obtained.

Molecular weight calculated for C| H N O C l=3055 Molecular weight found by potentiometric determination in acetic acid by perchloric acid =308 4-tetrahydro) 7-naphthyl] 4-amino 2-methyl phenol is prepared in accordance with the following reaction:

0505 WHEY 11g) of sodium hydrosulfite of 75 percent purity is dissolved in 145 cc of 1.25 N soda solution. To this resulting solution there is gradually added, with stirring and while keeping the temperature in the vicinity of 30, 0.02 mole (5.76 g) of N-[(6'-hydroxy 1-oxa 4'-aza 1', 2'3, 4-tetrahydro) 7'-naphthyl] 3- methyl benzoquinoneimine monohydrate in 30 cc of ethanol. when the addition is completed, the reaction,

20 #mixture very rapidly becdrn es colorless. Acetic acid is then added to it until neutrally thereby precipitating Ithe above diphenylamine which is then filtefed under nitrogen, washed in water and dried under vacuum for 5 hours at 4.30 g of pure product in monohydrate form, which melts at 194, are thus obtained.

Analysis Calculated for Found C% 62.07 61.73 61.96 H)? 6.20 6.3] 6.25 N% 9.65 9.42 9.68

EXAMPLE 24 Third method for preparing 4-hydroxy 2,6,3,

5-tetramethyl 2, 4'-diamino diphenylamine already described in Examples 6 and 7 is as follows: 0.00372 mole (l g) of N-[(2', 4-diamino 3', 5'-dimethyl) phenyl] 2,6-dimethyl benzoquinoneimine is dissolved in cc of absolute ethyl alcohol. Then palladium or barium sulfate (5 percent Pd/SO, Ba Englehard Industries) is added as the catalyst and the product is reduced in the usual way by hydrogen at ambient pressure. After 15 minutes, the alcohol solution has become completely colorless. This solution is then filtered to recover the catalyst and it is concentrated under vacuum and nitrogen up to 15 cc. 40 cc of water are then added and the above diphenylamine which is filtered and dried under vacuum exhibits a melting point of 251 and does not give a lowering of the melting point when used in mixture with the products prepared according to the processes described in Examples 6 and 7.

EXAMPLE 25 4-hydroxy 3,6,5-trimethyl 2, 4'-diam ino diphenylamine is prepared as follows:

NHz CH;

H: CH3

First phase A: PrepzFatioF of 4 hydr o xy 3,? trimethyl 2', 4-dinitro diphenylamine lnto 300 cc of absolute ethanol there are introduced, on the one hand, 0.04 mole (10.44 g) of 2,4 -dinitro 5- bromo toluene, and, on the other hand, 0.04 mole (5.48 g) of 2,5-dimethyl 4-amino phenol and 4.1 g of molten sodium acetate. The resulting mixture is heated to reflux for 5 hours with stirring and filtered hot to eliminate the inorganic salts. 300 cc of water are then added and the mixture cooled to 0 thereby precipitating 1 l g of 4-hydroxy 3, 6,5'-trimethyl 2', 4'-dinitro diphenylamine which are filtered and which, after recrystallization in ethanol, melt at l74.

Analysis Calculated for Found CISHISNIIOS iH7r 4.77 4.86 4.92

lNZ' 13.24 13.42 13.26

Second phase Preparation of 4-hydroxy 3,6,5- trimethyl 2, 4'-diamino diphenylamine 0.0714 mole (20 g) of sodium hydrosulfite of 75 percent purity is dissolved in 300 cc of a normal soda solution. To this resulting solution there is added gradually, 5 with good stirring, while keeping the temperature in the vicinity of 55, 0.01 mole (3.2 g) of the dinitro derivative obtained in the first phase, as described above. When the addition is completed and the reaction mixture is colorless, it is cooled and then neutralized with acetic acid to precipitate the above diphenylamine. After filtering, washing with water and drying under vacuum at 80 for 5 hours, the product melts at 214.

Molecular weight calculated for C l-1 N O 0.5 11 0 :2 15

Molecular weight found by potentiometric determination in acetic acid by perchloric acid =267 Calculated for Analysis Found EXAMPLE 26 4-hydroxy 2,3dimethyl 5-methoxy 2', 4-diamino diphenylamine is prepared as follows:

NH: CH3 CH3 Analysis Calculated for Found C 5H fl 6 Second phase Preparation of 4-hydroxy 2,3-

dimethyl 5'-methoxy 2, 4'-diamino diphenylamine 0.003 mole (l g) of the above dinitro derivative obtained in the first phase is dissolved in cc of ethyl acetate. 0.2 g of palladium on carbon (10% Pd on C 65 of Englehard Industries) is added and the product is reduced by hydrogen at ambient pressure. The solution troleum ether, 4-hydroxy 2,3-dimethyl 5'-methoxy 2', 4-diamino diphenylamine crystallizes, which is then filtered and dried under vacuum for several days. This product melts at 195.

The following hair dye composition is prepared:

Dye of Example 1 0.1 g Ethyl alcohol, 96 titer 20 g Water, g.s.p. 100 g Ammonia at 22 Be... q.s.p. pH 10 This hair dye composition when applied for 20 minutes to percent naturally white hair, imparts thereto an intense violine shade after rinsing and shampooing.

EXAMPLE 28 The following hair dye composition is prepared:

Dye of Example 10 0.1 g Ethyl alcohol, 96 titer 20 g Water, q.s.p. 100 g Ammonia at 22Be., q.s.p. pH 10 This hair dye composition when applied for 20 minutes to bleached hair, imparts thereto, after rinsing and shampooing, a very luminous intense parme shade.

EXAMPLE 29 The following hair dye composition is prepared:

Dye of Example 5 0.1 g Ethyl alcohol, 96 titer L 30 g Water, q.s.p. 100 g Ammonia at 22Be., q.s.p. pH 10 This hair dye composition when applied for 20 minutes to bleached hair, imparts thereto, after rinsing and shampooing, a silvery blue gray shade.

EXAMPLE 30 The following hair dye composition is prepared:

Dye of Example 6 0.1 g lsopropyl alcohol, 96 titer 40 g Water, q.s.p. 100 g Ammonia at 22Be., q.s.p. pH 9.5

v EXAMPLE 31 The following hair dye composition is prepared:

Dye of Example 3 0.15 g Ethyl alcohol. 96 titer 30 g Water, q.s.p. I g

The pH of the solution is 8 This hair dye composition when applied for IS minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, an intense purple violet shade.

EXAMPLE 32 The following hair dye composition is prepared:

Dye of Example 4 0.085 g Ethyl alcohol, 96 titer 20 g Water q.s.p. I00 g Ammonia at 22Be., q.s.p. pH 9 This hair dye composition when applied for 20 minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a slightly violet red shade with golden glints.

EXAMPLE 33 The following hair dye composition is prepared:

Dye of Example 6 Ethyl alcohol, 96 titer Water, q.s.p. 100 g Ammonia at 22Be., q.s.p. pH l0 This hair dye composition when applied for 20 minutes to bleached hair, imparts thereto, after rinsing and shampooing, a very intense purple violet shade.

EXAMPLE 34 The following hair dye composition is prepared:

Dye of Example 8 (in dihydrochloride form) 0.l65 g Ethyl alcohol, 96 titer 30 g Water. q.s.p. I00 8 Ammonia at 22' Be.. q,s.p. pH 9 This hair dye composition when applied for minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a very luminous mauve shade with pink glints.

EXAMPLE 35 The following hair dye composition is prepared:

Dye of Example 2 (in dihydrochloride, monohydrate 0.I5 g form) Ethyl alcohol. 96 titer 40 g Water, q.s.pv 100 g Ammonia at 22Be., q.s.p. pH 9.5

This hair dye composition when applied for minutes to bleached hair, imparts thereto, after rinsing and shampooing, a silvery turquoise blue shade.

EXAMPLE 36 The solution of Example 35 is applied for 20 minutes to 95 percent naturally white hair. After rinsing and shmpooing, a very luminous silver gray is obtained.

EXAMPLE 37 The following dye composition is prepared:

1% lactic acid solution, q.s.p. pH 5.5

This hair dye composition when applied for 20 minutes to bleached hair, imparts thereto, after rinsing and shampooing, a very strong violet shade.

EXAMPLE 38 The following hair dye composition is prepared:

Dye of Example 9 0| g Ethyl alcohol, 96 titer 25 g Water, q.s.p. lOO g 1% lactic acid solution, q.s.p. pH 7 This hair dye composition when applied for 20 minutes to percent naturally white hair, imparts thereto, after rinsing and shampooing, an ash blond shade with mauve glints.

EXAMPLE 39 The following hair dye composition is prepared:

Dye of Example I5 0.l g lsopropyl alcohol, 96 titer 30 g Water, q.s.p. I00 g Ammonia at 22 8a., q.s.p. pH I0 This hair dye composition when applied for IS minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a very luminous cyclamen shade.

EXAMPLE 40 The following hair dye composition is prepared:

Dye of Example 19 0.065 g Ethyl alcohol, 96 titer 20 g Water, q.s.p. I00 g I9? lactic acid solution, q.s.p. pH 7.5

This hair dye composition when applied for 20 minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a pearly glycine shade.

EXAMPLE 41 The following hair dye composition is prepared:

Dye of Example 13 0.15 g Ethyl alcohol, 96 titer 50 g Water, q.s.p. I00 g l7r lactic acid solution, q.s.p, pH 7 This hair dye composition when applied for 20 minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, an iridescent violet pink shade.

EXAMPLE 42 The following hair dye composition is prepared:

Dye of Example I6 0.03 g Ethyl alcohol, 96 titer 30 g Water. q.s.p. I00 g 1% lactic acid solution. q.s.p. pH 6 This hair dye composition when applied for 30 minutes to bleached hair, imparts thereto, after rinsing and shampooing, a cyclamen coloring.

EXAMPLE 43 The following hair dye composition is prepared:

Dye of Example I 0.005 g Ethyl alcohol, 96 titer 20 g Water, q.s.p. I g

1% lactic acid solution, q.s.p. pH 6.5

This hair dye composition when applied for min utes to bleached hair, imparts thereto, after rinsing and shampooing, a bright pink shade with golden glints.

EXAMPLE 44 The following hair dye composition is prepared:

Dye of Example 12 0.04 g Ethyl alcohol, 96 titer 30 g Water, q.s.p, I00 g l71 lactic acid solution, q.s.p. pH 7.5

This hair dye composition when applied for minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a pearly rose shade.

EXAMPLE 45 The following hair dye composition is prepared:

Dye of Example 17 (H g Butylglycol 5 g Lauryl alcohol oxyethylenated with l0.5 moles of 5 g ethylene oxide Water, q.s.p I00 g Ammonia at 22 80.. q.s.p. pH 9 This hair dye composition when applied for 20 minutes to bleached hair, imparts thereto, after rinsing and shampooing, a golden blond shade with pink glints.

EXAMPLE 46 The following hair dye composition is prepared:

Dye of Example 2i 0.075 g Ethyl alcohol, 96 titer g Water, q.s.p. I00 g I71 lactic acid solution, q.s.p. pH 6 This hair dye composition when applied for 20 minutes to bleached hair, imparts thereto, after rinsing and shampooing, a turquoise blue shade.

EXAMPLE 47 The following hair dye composition is prepared:

Dye of Example 22 0.09 g Ethyl alcohol, 96 titer 30 g Water, q.s.p. I00 g l7r lactic acid solution. q.s.p. pH 5.5

This hair dye composition when applied for 20 minutes to bleached, hair, imparts thereto, after rinsing and shampooing, a pale blue green shade with golden glints.

EXAMPLE 48 The following hair dye composition is prepared:

Ammonia at 22 Be., q.s.p. pH 9 This hair dye composition when applied for 20 minutes to natural medium brown hair, imparts thereto, after rinsing and shampooing, a dark brown coloring with violine glints.

EXAMPLE 49 The following hair-setting lotion composition is prepared:

Dye of Example I7 0.05 g Vinyl acetate-crotonic acid copolymer vinyl 2 g acetate, l0% crotonic acid, molecular weight 45,000 to 50,000)

Ethyl alcohol, 96 titer Water, q.s.p.

Ammonia at 22 Be., q.s.p pH 6.5

This hair-setting lotion when applied to bleached hair imparts thereto a golden blond shade with pink glints.

EXAMPLE 50 The following hair-setting lotion composition is prepared:

Dye of Example 23 0.18 g 4-hydroxy 2,4-diamino S-methyl diphcnylaminc 0.05 g dihydrochloride Vinyl acctate-crotonic acid copolymer (90% vinyl 2 g acetate, I07: crotonic acid molecular weight 45,000

Ethyl alcohol, 96 titer 50 g Water, q.s.p. I00 g Ammonia at 22 Be., q.s.p. pH 8.5

This hair-setting lotion when applied to bleached hair, imparts thereto a light golden bronze shade.

EXAMPLE 51 The following hair-setting lotion composition is prepared:

Dye of Example l0 0.005 g Vinyl acetate-crotonic acid copolymer (90% vinyl 2 g acetate, I07: crotonic acid, molecular weight 45,000 to 50,000)

lsopropyl alcohol, 96 titer Water, q.s.p.

Ammonia at 22 Be., q.s.p. pH 8 50 g I00 g This hair-setting lotion when applied to bleached hair, imparts thereto a pearly blond shade with pink glints.

EXAMPLE 52 The following hair-setting lotion composition is prepared:

Dye of Example 19 0.055 g Vinyl acetate-crotonic acid copolymer (90% vinyl 2 g acetate, 10% crotonic acid, molecular weight 45,000 to 50.000)

Ethyl alcohol, 96 titer Water, q.s.p.

Ammonia at 22 Be, qts.p. pH 7 50g lOOg This hair-setting lotion when applied to 95 percent naturally white hair, imparts thereto, a silvery gray shade with light mauve glints.

EXAMPLE 53 The following hair-setting lotion composition is prepared:

Dye of Example 9 0.065 g Vinyl acetate-crotonic acid copolymer (90% vinyl 2 g acetate, 10% crotonic acid molecular weight 45,000

Ethyl alcohol, 96 titer 50 g Water, q.s.p. I g

Ammonia at 22 Be., q.s.p pH 8.5

This hair setting lotion when applied to bleached hair, imparts thereto a pearly ash blond shade.

EXAMPLE 54 The following hair-setting lotion composition is prepared:

Dye of Example 4 0| g Vinyl acetate-crotonic acid copolymer (90% vinyl l g acetate, crotonic acid, molecular weight 45,000

Ethyl alcohol, 96 titer 25 g Water, q.s.pv I00 g Ammonia at 22 Be., q.s.p. pH 8.5

This hair-setting lotion when applied to bleached hair, imparts thereto a pearly pink shade.

EXAMPLE 55 The following hair-setting lotion composition is prepared:

Dye of Example 10 0.5 g Vinyl acetate-crotonic acid copolymer (9071 vinyl 2 g acetate, 10% crotonic acid, molecular weight 45,000 to 50,000)

Ethyl alcohol, 96 titer Water. q.s.p.

Triethanolamine, q.s.p. pH 7.5

This hair-setting lotion composition when applied to bleached hair, imparts thereto a very intense mauve shade.

EXAMPLE 56 The following hair-setting lotion composition is prepared:

Dyc of Example 13 0.08 g Vinyl acetatc-crotonic acid copolymer (90% vinyl 2 g acetate. 10'71 crotonic acid. average molecular weight Ethyl alcohol, 96 titer 50 g Water, q.s.p. I00 g Ammonia at 22 Be., q.s.pv pH 6 This hair-setting lotion when applied to bleached hair imparts thereto a pale pink shade with golden glints.

EXAMPLE 5 7 The following hair-setting lotion composition is prepared:

Dye of Example 23 0.08 g

Ammonia at 22 Be., q.s.p. pH 6 This hair-setting lotion when applied to bleached hair imparts thereto a pale golden green shade.

EXAMPLE 58 The following hair-setting lotion composition is prepared:

Dye of Example 2 0.l l g Vinyl acetate-crotonic acid copolymer vinyl 2 g acetate, [0% crotonic acid, molecular weight 45,000

Ethyl alcohol, 96 titer 50 g Water, q.s.p. I00 g Ammonia at 22 Be., q.s.p. pH 9 This hair-setting lotion when applied to bleached hair imparts thereto a silvery beige gray shade.

EXAMPLE 59 The following hair-setting lotion composition is prepared:

Dye of Example 5 0| g Vinyl acetate-crotonic acid copolymer (50% vinyl 2 g acetate, [07: crotonic acid, molecular weight 45,000 to 50,000)

Ethyl alcohol, 96 titcr Water, q.s.p.

Ammonia at 22Be., q.s.p. pH 9 This hair-setting lotion when applied to bleached hair imparts thereto a pearly pink blond shade.

EXAMPLE 60 The following hair-setting lotion composition is prepared:

Dye of Example 21 0.05 g Vinyl acetate-crotonic acid copolymer (90% vinyl 2 g acetate, 10% crotonic acid, molecular weight 45,000 to 50,000)

lsopropyl alcohol, 96 titer Water, q.s.p.

Ammonia at 22Be., q.s.p. pH 7 50 g I00 g This hair-setting lotion when applied to bleached hair imparts thereto a light pearly turquoise blue shade.

EXAMPLE 61 The following hair-setting lotion composition is prepared:

Dye of Example l5 0.055 g Vinyl acetatewmtonic acid copolymer (90% vinyl l.5 g acetate, 10% crotonic acid, molecular weight 45,000

Ethyl alcohol, 96 titer 35 g Water, q.s.p. 100 g Ammonia at 22Be., q.s.p. pH 9 This hair-setting lotion when applied to bleached hair imparts thereto a pearly rose mauve shade.

EXAMPLE 62 The following hair-setting lotion composition is prepared:

Dye of Example 4 0.005 g Vinyl acetate-crotonic acid copolymer (vinyl acetate 2 g 90%, crotonic acid molecular weight 45,000 to 50,000 Ethyl alcohol, 96 titer 50 g 10 Water, q.s.p. l00 g Ammonia at 22Be., q.s.p. pH 8.5

This hair-setting lotion when applied to bleached hair imparts thereto a golden blond shade with pink glints.

EXAMPLE 63 The following hair dye composition is prepared:

Dye of Example 20 O.l5 g Ethyl alcohol, 96 titer 30 g Water, q.s.p. I00 g Ammonia at 22Be., q.s.p. pH 9 This hair dye composition when applied for 20 min- 25 utes to bleached hair imparts thereto, after rinsing and shampooing, a light turquoise blue shade.

EXAMPLE 64 The following hair-setting lotion composition is prepared:

Dye of Exmaple l4 0.045 g Vinyl acetate-crotonic acid copolymcr (90% vinyl 2 g acetate, 10% crotonic acid, molecular weight 45,000 m 50,000 Ethyl alcohol, 96 titer 50 g Water, q.s.p. l00 g Ammonia at 2ZBe., q.s.p. pH 7 This hair-setting lotion when applied to bleached hair imparts thereto a pale green shade.

EXAMPLE 65 The following hair dye composition is prepared:

Dye of EXAMPLE 18 0.105 g Ethyl alcohol, 96 titer 20 g Water, q.s.p. I00 g Ammonia at 22Be., q.s.p. pH 9 This hair dye composition when applied for 20 minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a rose beige shade.

EXAMPLE 66 The following hair dye composition is prepared:

Dye of Example 18 0.1 g 2.6-diamino 4-N,N-diethylamino-2 phenol 0.03 g trihydrochloride Ethyl alcohol. 96 titer 20 g Water. q.s.p. I00 g Ammonia at 2'2Be.. q.s.p. pH 9 This hair dye composition when applied for 20 minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a dark copper blonde shade.

EXAMPLE 67 The follwing hair dye composition is prepared:

Dye of Example 8 0.] g Z-amino 4-methoxy phenol hydrochloride 0.02 g 4.4-dihydroxy 3,5-dimethyl diphenylamine 0.06 g Ethyl alcohol, 96 titer 20 g Water, q.s.p. I00 g Ammonia at 22Be., q.s.p. pH 9 This hair dye composition when applied for 20 minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a slightly mauve silvery gray shade.

EXAMPLE 68 The following hair dye composition is prepared:

Dye of Example 2 0.12 g Ethyl alcohol, 96 titer 30 g 20 volume hydrogen peroxide 50 g Water, q.s.p. 100 g Ammonia at 22Be., q.s.p. pH 9 This hair dye composition when applied for 20 minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a silvery blue gray shade.

EXAMPLE 69 The following hair dye composition is prepared:

Dye of Example 25 0.055 g Ethyl alcohol. 96 titer 20 g Water, q.s.p. I00 g Ammonia at 22Bc., q.s.p. pH l0 This hair dye composition when applied for 20 minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a silvery glycine shade.

EXAMPLE 70 The following hair dye composition is prepared:

Dye of Example 26 0.08 g Ethyl alcohol. 96 titer 30 g Water, q.s.p. I00 g The pH of this composition is 8 This hair dye composition when applied for 20 minutes to bleached hair, imparts thereto, after rinsing and shampooing, an intense cyclamen shade.

EXAMPLE 71 The following hair dye composition is prepared:

Dye of Example 8 0.035 g Nitroorthophenylenediamine 0.08 Ethyl alcohol, 96 titer 20 g Water, q.s.p. I00 g Ammonia at 22Be., q.s.p. pH 9.5

This hair dye composition when applied for 20 minutes to percent naturally white hair, imparts thereto, after rinsing and shampooing, a very luminous bronze green shade.

EXAMPLE 72 The following hair dye composition is prepared:

Dye of Example 0.025 g N-[(2',4'-diamino 5'-methyl) phenyl] 0.075 g benzoquinoneimine Nitrometaphenylenediamine 0.04 g Ethyl alcohol, 96 titer g Water. q.s.p. I00 g Ammonia at 22Be., q.s.p. pH 9.5

a. a diphenylamine of the formula wherein R. and R each independently represent a member selected from the group consisting of hydrogen, halogen and lower alkyl with the proviso that at least one of R, and R is other than hydrogen; R R, and R each independently are selected from the group consisting of hydrogen, lower alkyl containing one to four carbon atoms, hydroxy lower alkyl containing one to four carbon atoms and methoxy R is selected from the group consisting of hydrogen, lower alkyl containing one to four carbon atoms and hydroxy lower alkyl containing one to four carbon atoms; R, is selected from the group consisting of hydrogen, lower alkyl containing one to four carbon atoms and hydroxy lower alkyl containing one to four carbon atoms; and Z is selected from the group consisting of amino, acylamino and hydroxy; and

b. the acid salts of said diphenylamine of (a).

2. The composition of claim 1 wherein said diphenylamine is 4-hydroxy-3,5,3',5'-tetramethyl-2, 4'-diamino diphenylamine.

3. The composition of claim 1 wherein said diphenylamine is present in amounts of 0.002-2 percent by weight of said composition.

4. The composition of claim 1 having a pH between 4 and ll.

5. The composition of claim 1 which also includes a dyevselected from the group consisting of orthoand para-phenylenediamines, orthoand paraaminophenols, other leuco derivatives of indoanilines, indamines or indophenols, and direct dyes.

6. The composition of claim 1 wherein said alcohol is a glycol in amounts of l to 6 percent by weight.

7. The composition of claim 6 wherein said glycol is selected from the group consisting of propyleneglycol and butylglycol. v

8. The composition of claim 1 wherein said alcohol is a low molecular weight alcohol in amounts of 20 to percent by weight.

9. The composition of claim 8 wherein said low molecular weight alcohol is selected from the group consisting of ethanol and isopropanol.

10. The composition of claim 1 wherein said solvent is an aqueous alcohol solution and which also includes a cosmetic resin.

11. The composition of claim 10 wherein said cosmetic resin is selected from the group consisting of polyvinylpyrrolidone, copolymer of crotonic acid-vinyl acetate, copolymer of vinylpyrrolidone and vinyl acetate and copolymer of maleic anhydride and butylvinyl ether.

12. The composition of claim 10 wherein said cosmetic resin is present in amounts of l to 3 percent by weight.

13. A process of dyeing keratinous fibers comprising impregnating said fibers with the composition of claim 1, permitting said composition to remain in contact with said fibers for a time ranging from about 10 to 30 minutes, rinsing said fibers and drying said fibers.

14. A process for treating human hair comprising applying to hair previously washed and rinsed, a composition defined in claim 10, rolling said hair up on curlers and drying said hair.

15. The process of claim 13, comprising adding to the composition before its application, either hydrogen peroxide in an amount of 4 to 12 percent in weight or an equivalent quantity of another oxidizing agent, of

said composition.

Patent No. 3,7B7p174 .5 UNITED STATES PATENT OFFICE v CERTIFICATE OF CORRECTION -Dated J anuarL 22, 1974 s; Andree Bugaut Grego ire Ka Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

' Under the heading "Foreign Application Priority Data", add

--Luxembourg 63,527,, ul 14, 1971,.

Signed and s ea'ledthis 16th day ofJulylg-mr (SEAL) Attest:

' MCCOY M. GIBSON, JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents 

2. The composition of claim 1 wherein said diphenylamine is 4-hydroxy-3,5,3'',5''-tetramethyl-2'', 4''-diamino diphenylamine.
 3. The composition of claim 1 wherein said diphenylamine is present in amounts of 0.002-2 percent by weight of said composition.
 4. The composition of claim 1 having a pH between 4 and
 11. 5. The composition of claim 1 which also includes a dye selected from the group consisting of ortho- and para-phenylenediamines, ortho- and paraaminophenols, other leuco derivatives of indoanilines, indamines or indophenols, and direct dyes.
 6. The composition of claim 1 wherein said alcohol is a glycol in amounts of 1 to 6 percent by weight.
 7. The composition of claim 6 wherein said glycol is selected from the group consisting of propyleneglycol and butylglycol.
 8. The composition of claim 1 wherein said alcohol is a low molecular weight alcohol in amounts of 20 to 70 percent by weight.
 9. The composition of claim 8 wherein said low molecular weight alcohol is selected from the group consisting of ethanol and isopropanol.
 10. The composition of claim 1 wherein said solvent is an aqueous alcohol solution and which also includes a cosmetic resin.
 11. The composition of claim 10 wherein said cosmetic resin is selected from the group consisting of polyvinylpyrrolidone, copolymer of crotonic acid-vinyl acetate, copolymer of vinylpyrrolidone and vinyl acetate and copolymer of maleic anhydride and butylvinyl ether.
 12. The composition of claim 10 wherein said cosmetic resin is present in amounts of 1 to 3 percent by weight.
 13. A process of dyeing keratinous fibers comprising impregnating said fibers with the composition of claim 1, permitting said composition to remain in contact with said fibers for a time ranging from about 10 to 30 minutes, rinsing said fibers and drying said fibers.
 14. A process for treating human hair comprising applying to hair previously washed and rinsed, a composition defined in claim 10, rolling said hair up on curlers and drying said hair.
 15. The process of claim 13, comprising adding to the composition before its application, either hydrogen peroxide in an amount of 4 to 12 percent in weight or an equivalent quantity of another oxidizing agent, of said composition. 